Amine salts of oxyalkylenated hydroxyhydrocarbon thiophosphates



United States Patent 3,340,329 AMINE SALTS 0F OXYALKYLENATED HY-DROXYHYDROCARBON THIOPHOSPHATES Anthony J. Guarnaccio, Niles, and EdwinJ. Latos, Chicago, Ill., assignors to Universal Oil Products Company,Des Plaines, 111., a corporation of Delaware No Drawing. Filed Dec. 12,1963, Ser. No. 330,003

11 Claims. (Cl. 260-925) This application relates to novel compositionsof matter comprising amine salts of oxyalkylenated hydroxyhydrocarbonthiophosphates and to the use thereof as additives to organicsubstrates.

As will be set forth in detail hereinafter, the novel compound of thepresent invention is particularly advantageous for use as an additive tolubricating compositions comprising a major proportion of an oil oflubricating viscosity. A specific example of such a lubricatingcomposition is E.P. (extreme pressure) lubricating oil used, forexample, in the lubrication of hypoid gears, in which service the oilmust meet the severe requirements of high torque-low speed, lowtorque-high speed and high torque-high speed conditions. Theserequirements are even more severe because such oils must performsatisfactorily for long periods of time which may be as high as 100,000miles or more and even for the life of the vehicle.

In a preferred embodiment the novel compound of the present invention isbelieved to be of the following formula:

where O is oxygen, P is phosphorus, S is sulfur, H in hydrogen, X isselected from the group consisting of oxygen and sulfur, n is an integerof from 1 to 40, R is a hydrocarbon group, R is alkylene, A is amine andB is selected from the group consisting of hydrogen, the same as thebracketed group and the same as A. When X is oxygen, B is the same asthe bracketed group. When X is sulfur, B is hydrogen or the same as A-.

A preferred embodiment is illustrated in the formula set forth below:

where O is oxygen, P is phosphorus, S is sulfur, H .s hydrogen, N isnitrogen, B is the same as the bracketed group, n is an integer of from1 to 40, R is a hydrocarbon group, R is alkylene, R" is hydrocarbon orsubstituted hydrocarbon group, and R' is hydrogen, hydrocarbon orsubstituted hydrocarbon group.

In a preferred embodiment, R is selected from alkylphenyl and aliphaticgroups. In the alkylphenyl species, 1, 2 or 3 alkyl groups of from 4 to30 and, more particularly, from 6 to 15 carbon atoms each, will beattached to the phenyl ring. Illustrative preferred alkylphenyl groupsinclude hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl,decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl,tetradecylphenyl, pentadecylphenyl, etc., dihexylphenyl, diheptylphenyl,dioctylphenyl, dinonylphenyl, didecylphenyl, diundecylphenyl,didodecylphenyl, etc., trihexylphenyl, triheptylphenyl, trioctylphenyl,trinonylphenyl, tridecylphenyl, etc. It is understood that the alkylgroups attached to the phenyl group may be of 3,340,329 Patented Sept.5, 1967 primary, secondary or tertiary configuration, the primary andsecondary configurations generally being preferred. In anotherembodiment the alkylphenyl radical may contain one or more alkyl groupscontaining 4 to 30 carbon atoms and one or more alkyl groups containingless than 4 carbon atoms and selected from methyl, ethyl and propyl.When one alkyl group is attached to the phenyl ring, it preferably is inthe position para to the oxygen. When two alkyl groups are attached tothe phenyl ring, they preferably are in the 2,4- or 3,5-positions.

Where R is an aliphatic group, it preferably contains from 6 to 40carbon atoms and, more particularly, from 10 to 30 carbon atoms.Illustrative preferred aliphatic groups include decyl, undecyl, dodecyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oc-tadecyl,nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl,pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl,etc. In general, it is preferred that the aliphatic group is saturated.In another embodiment, the aliphatic group may be unsaturated and willbe selected from olefinic radicals corresponding to the saturatedradicals hereinbefore specifically set forth. The aliphatic group may bestraight chain or may contain branching in the chain.

R in the above formula is an alkylene group and may contain from 1 to 10and preferably from 2 to 4 carbon atoms per group. The preferredalkylene radicals thus are ethylene, propylene and butylene. Ashereinbefore set forth, n is an integer of from 1 to 40 and preferablyof from 2 to 15.

As hereinbefore set forth, the novel additive of the present inventionis an amine salt of an oxyalkylenated hydroxyhydrocarbon thiophosphate.Referring to the above general formula, when X is sulfur and B is hydro:gen or the same as A, the additive comprises the amine salt of themono-(oxyalkylenated hydroxyhydrocarbon) thiophosphate. When X is oxygenand B in the above formula is the same as the bracketed group(oxyalkylenated hydroxyhydrocarbon), the additive of the presentinvention comprises the amine salt of the di-(oxyalkylenatedhydroxyhydrocarbon)thiophosphate. It is understood that a mixture of theamine salt of the mono= (oxyalkylenated hydroxyhydrocarbon)thiophosphate and of the amine salt of the di-(oxyalkylenated hydroxy-.hydrocarbon) thiophosphate may be employed and also that a mixture ofdifierent amines may be used in preparing these additives.

Any suitable amine may be used and contains from 2 to 50 carbon atoms ormore and preferably from 8 to 20 carbon atoms. The amine may be amonoamine or polyamine. Preferred monoamines include octyl amine, nonylamine, decyl amine, undecyl amine dodecyl amine, tridecyl amine,tetradecyl amine, pentadecyl amine, hexaa decyl amine, heptadecyl amine,octadecyl amine, nonadecyl amine, eicosyl amine, etc. The amines may beprepared from fatty acid derivatives and, thus, may comprise tallowamine, hydrogenated tallow amine, lauryl amine, stearyl amine, oleylamine, linoleyl amine, coconut amine, soya amine, etc.

Of the polyamines, N-alkyl diaminoalkanes are prea ferred. Aparticularly preferred amine of this class comprises anN-alkyl-1,3-diaminopropane in which the alkyl group contains from about8 to about 25 carbon atoms. A number of N-alkyl diaminoalkanes of thisclass are available commercially, such as Duomeen T and Diam 26 in whichthe alkyl group is derived from tallow and contains from about 12 toabout 20 carbon atoms per group and mostly 16 to 18 carbon atoms. OtherN-alkyL 1,3-diaminopropanes may be prepared to contain any number ofcarbon atoms desired in the alkyl group and thus the alkyl group isselected from hexyl, heptyl, octyl,

nonyl, decyl, unclecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.

While the N-alkyl-l,3-diaminopropanes are preferred, it is understoodthat other suitable N-alkyl diaminoalkanes may be employed. Illustrativeexamples include N-alkyl- 1,2-diaminoethane, N-alkyl-1,2-diaminopropane,N-alkyl- 1,2-diaminobutane, N-alkyl-l,3-diaminobutane, N-alkyl-l,4-diaminobutane, N-alkyl1,2-diaminopentane, N-alkyl-l, B-diaminopentane,N-alkyl-l,4-diaminopentane, N-alkyl-l, S-diaminopentane,N-alkyl-1,Z-diaminohexane, N-alkyl-l, 3-diaminohexane,N-alkyl-1,4-diaminohexane, N-alkyl-l, S-diaminohexane,N-alkyl-l,6-diaminohexane, etc. Other polyamines includeethylenediamine, propylenediamine, butylenediamine, pentylenediamine,hexylenediamine, heptylenediamine, octylenediamine, etc.,diethylenetriamine, dipropylenetriamine, dibutylenetriamine,dipentylenetriarnine, dihexylenetriamine, dipheptylenetriamine,dioctylenetriamine, etc., triethylenetetraamine, tripropylentetraamine,tributylenetetraamine, tripentylenetetraamine, trihexylenetetraamine,triheptylenetetraamine, trioctylenetetraamine, etc.,tetraethylenepentaamine, tetrapropylenepentaamine,tetrabutylenepentaamine, tetrahexylenepentaamine,tetraheptylenepentaamine, tetraoctylenepentaamine, etc.,pentaethylenehexaamine, pentapropylenehexaamine, pentabutylenehexaamine,pentapentylenehexaamine, pentahexylenehexaamine,pentaheptylenehexaamine, pentaoctylenehexaamine, etc.

In other embodiment the amine is an aromatic amine. Aromatic monoaminesinclude aniline, toluidines, xylidines, etc., naphthylamine,anthracylamine, rosin amine, etc., as well as the N-monoandN,N-di-alkylated aromatic amines in which the alkyl group or groupscontain from 1 to carbon atoms or more. Illustrative examples of suchcompounds include N-methylaniline, N,N-di-methylaniline, N-ethylaniline,N,N-di-ethylaniline, N-propylaniline, N,N-di-pyropylaniline,N-butylaniline, N,N-dibutylaniline, N-amylaniline, N,N-di-amylaniline,N-hexylaniline, N,N-di-hexylaniline, N-heptylaniline,N,N-diheptylaniline, N-octylaniline, N,N-di-octylaniline,N-nonylaniline, N,N-di-nonylaniline, N-decylaniline,N,N,-didecylaniline, N-undecylaniline, N,N-di-undecylaniline, N-dodecylaniline, N,N-di-dodecylaniline, etc., as Well as thecorresponding substituted toluidines, xylidines, naphthylamines,anthracylamines, etc.

In still another embodiment the amine may contain halogen as, forexample, in compounds such as chloroaniline, 2,3-dichloroaniline,2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline,3,4-dichloroaniline, 3,5-dichloroaniline, bromoaniline,2,3-dibro-moaniline, 2,4-dibromoaniline, 2,5-dibromoaniline,2,6-dibromoaniline, 3, 4-dibromoaniline, 3,5-dibromoaniline, etc.

In another embodiment the aromatic amine is a diarylamine including, forexample, diphenylamine, aminodiphenylamine, diaminodiphenylamine,dinaphthylamine, aminodinaphthylamine, diaminodinap-hthylamine, etc. Inthe polyamino aromatic compounds, the nitrogen atoms may be in theposition ortho-, metaor parato each other. The amino ordiaminodiphenylamines may contain alkyl groups attached to one or bothnitrogen atoms and the alkyl groups may contain from 1 to or more carbonatoms each. Illustrative compounds includep,p-di-methylaminodiphenylamine, p,p'-di-ethylaminodiphenylamine, p, pdi propylaminodiphenylamine, p,p'-di-butylaminodiphenylamine,p,p'-di-amylaminodiphenylamine, p,p'-dihexylaminodiphenylamine, p,p'di-heptylaminodiphenylamine, p,p-di-octylaminodiphenylamine,p,p'-di-nonylaminodiphenylamine, p,p di-decylaminodiphenylamine, etc.,o,p'-di-methylaminodiphenylamine, o,p'-di-ethylaminodiphenylamine,o,p'-di-propylaminodiphenylamine, o, p-di-butylaminodiphenylamine,-o,p'-di-amy1aminodiphenylamine, o,p'-di-hexylaminodiphenylamine,o,p'-di-heptylaminodiphenylamine, o,p'-di-octylaminodiphenylamine, o, pdi-nonylaminodiphenylamine, o,p-di-decylarninodiphenylamine, etc.,N-alkyldiaminodiphenylamine, N,N,N-

trialkyldiaminodiphenylamine, N,N,N',N-tetralkyldiaminodiphenylamine,etc.

In still another embodiment the amine comprises such compounds asaminodiphenyl ether, N-alkylaminodiphenyl ether,N,N-dialkylaminodiphenyl ether, N,N,N'-trialkyl aminodiphenyl ether,N,N,N'N'-tetralkylaminodiphenyl ether, aminodiphenyl sulfide,N-alkylaminodiphenyl sulfide, N,N-dialkylaminodiphenyl sulfide,N,N,N'-trialkylaminodiphenyl sulfide, N,N,N,N'-tetralkylaminodiphenylsulfide, aminodiphenylmethane, N-alkylaminodiphenylmethane,N,N'-dialkylaminodiphenyhnethane, N,N,N'- trialkylaminodiphenylmethane,N,N,N',N-tetralkylaminodiphenylmethane, aminodiphenylethane,N-alkylaminodiphenylethane, N,N-dialkylaminodiphenylethane, N,N,N'-trialkylaminodiphenylethane, N,N,N,N'-tetralkylaminodiphenylethane,aminodiphenylpropane, N-alkylaminodiphenylpropane,N,N'-dialkylaminodiphenylpropane, N,N, N trialkylaminodiphenylpropane,N,N,N',N'-tetralkylaminodiphenylpropane, aminodiphenylbutane,N-alkylaminodiphenylbutane, N,N'-dialkylaminodiphenylbutane, N,N,N'trialkylaminodiphenylbutane, N,N,N',N-tetralkylaminodiphenylbutane,etc., in which the alkyl group or groups contain from 1 to 20 or morecarbon atoms each.

In still another embodiment the amine may contain other substituents andparticularly sulfur. The additional sulfur in the amine and,accordingly, in the final product may be of advantage when the productis used as an additive in lubricating oil or other substrate in whichadditional sulfur is desired. In one embodiment the sulfurcontainingamine is prepared by reacting carbon disulfide with the amine, andparticularly with an N-alkylated or N,N-di-alkylated alkylene polyamine.Particularly preferred substituted amines in this embodiment include theproduct formed by reacting carbon disulfide with N,N'-dialkyl-ethylenediamine or with N ,N -dialkyl-diethylenetriamine. Thereaction is effected by dissolving the amine in a suitable solvent suchas benzene, toluene, etc., pentane, hexane, heptane, etc., cooling thesolution to about 50 F. or lower and gradually adding an equal moleratio of carbon disulfide dissolved in a suitable solvent and preferablythe same solvent as used to dissolve the amine. The reaction is highlyexothermic and the temperature is controlled by cooling in an ice bathor otherwise. In most cases the reaction mixture solidifies, apparentlyforming an inert salt. The reaction mixture is heated to a temperatureof from about 300 to about 350 F. to remove the solvent and to eliminatehydrogen sulfide, resulting in the formation of the correspondingimidazolidinethione. The product is recovered as an amber clear liquid.It is understood that other sulfur-containing amines which react withthe oxyalkylenated hydroxyhydrocarbon thiophosphate may be used inaccordance with the present invention.

It is understood that a mixture of amines may be employed and that thedifferent amines are not necessarily equivalent, but all of them willserve to produce effective additives.

The compound of the present invention is prepared in any suitablemanner. In a preferred method, the hydroxyhydrocarbon, includingparticularly alkylphenol or aliphatic alcohol, is oxyalkylenated byreacting with alkylene oxide, including particularly ethylene oxide, inthe molar ratios to produce. an oxyalkylenated hydroxyhydrocarboncontaining the oxyalkylene group in the desired proportion. Ashereinabove set forth, in a preferred embodiment the additive containsfrom 2 to 15 oxyalkylene groups. The oxyalkylenation is effected in anysuitable manner and generally will be conducted at a temperature of fromabout room temperature to about 350 F. and more particularly from about200 to about 300 F. When polyoxyalkylenation is desired, the reaction iseffected in the presence of a catalyst such as sodium hydroxide,potassium hydroxide, tertiary amine, quaternary hydroxide, etc. When theoxyalkylenation is to be limited to the addition of one oxy group, thecatalyst is used with the alkanols but may be omitted with thealkylphenols. Superatmospheric pressure may be employed, which may rangefrom to 1000 pounds or more.

The oxyalkylenated hydroxyhydrocarbon then is reacted in any suitablemanner with phosphorus pentasulfide or other suitable phosphorus sulfideto form the desired phosphate. At the present time there are differentschools of thought as to the structure of phosphorus pentasulfide. It isbelieved to be P 8 but also has been expressed as P 8 Various structureshave been proposed including a polymeric cage-like configuration.Regardless of the exact structure of this compound, phosphoruspentasulfide is available commercially and is used for reaction with theoxyalkylenated hydroxyhydrocarbon in the manner herein set forth. In theinterest of simplicity, phosphorus pentasulfide is also referred to inthe present specifications as P 8 with the understanding that this isintended to cover the phosphorus pentasulfide available commercially orprepared in any suitable manner.

In a preferred embodiment the compound of the present invention is anamine salt of a di-(oxyalkylenated hydroxyhydrocarbon)-dithiophosphate(B in the above formula corresponding to the bracketed group) and isprepared by the reaction of four mole proportions of the oxyalkylenatedhydroxyhydrocarbon with one mole proportion of P 8 Generally, an excessof P 5 is used in order to insure complete reaction, which excessusually will not be above about 25% by weight of the stoichiometricamount of P 8 The reaction conveniently is effected by heating theoxyalkylenated hydroxyhydrocarbon and, with intimate stirring, addingthe P 8 thereto, preferably in in cremental portions. The reaction iseffected by refluxing the mixture of reactants to effect formation ofthe di-(oxyalkylenated hydroxyhydrocarbon) dithiophosphate with theliberation of one mole proportion of hydrogen sulfide.

The reaction preferably is effected in the presence of a solvent and thetemperature of refluxing accordingly will depend upon the specificsolvent used. Any suitable solvent may be employed. Preferred solventscomprise aromatic hydrocarbons and include particularly benzene. Whenusing benzene as the solvent, the refluxing temperature will be in theorder of 175 F. Other aromatic solvents include toluene, xylene, ethylbenzene, cumene, etc., or mixtures thereof. In another embodiment thesolvent may comprise a paraflinic hydrocarbon or mixtures thereof whichpreferably are selected from hexane, heptane, octane, nonane, decane,undecane, dodecane, etc. As herein before set forth, the refluxingtemperature will depend upon the particular solvent employed and thusmay range from about 140 and preferably should not exceed about 215 F.The reaction maybe effected at atmospheric pressure or, when desired, atsubatmospheric pressure or superatmospheric pressure.

Hydrogensulfide is formed in the above reaction and preferably iscontinuously removed from the reaction zone. After completion of thereaction, the reaction mass may be filtered to remove unreacted P 8 ifany. In one embodiment the product may be recovered in solution in thebenzene or other solvent or, when desired, the benzene solvent may beremoved in any suitable manner such as by distillation, preferably undervacuum. The di- (oxyalkylenated hydroxyhydrocarbon)-dithiophosphate isrecovered as a liquid of medium viscosity.

While the di-(oxyalkylenated hydroxyhydrocarbon)-dithiophosphate is apreferred reactant for forming the amine salt, it is understood that theuse of the mono- (oxyalkylenated hydroxyhydrocarbon) dithiophosphatealso is comprised Within the scope of the present invention, as well asthe monoand/or di-(oxyalkylenated hydroxyhydrocarbon)-monothiophosphate.The latter compound may be prepared, for example, by reacting di-(oxyalkylenated hydroxyhydrocarbon)-phosphite or the sodium salt thereofwith free sulphur.

As hereinbefore set forth, the novel additive of the present inventionis the amine salt. The amine salt is prepared in any suitable manner andis readily prepared by slowly adding the amine to the free acid form ofthe thiophosphate with intimate stirring. When the amine is a solid, itmay be heated to melt the same. The reaction is effected at any suitabletemperature, and preferably as low as practical. The temperature,therefore, preferably is within the range of from room temperature to250 F. and more particularly to 150 F. In general, the neutral salt ispreferred and is prepared by using equivalent amine and acid groups.Accordingly, this will depend upon whether a monoamine or polyamine isused and whether the monoor di (oxyalkylenated hydroxyhydrocarbon)thiophosphate is used in preparing the .salt. When the basic salt isdesired, an excess of amine per acid group will be used and, when theacid salt is desired, a deficiency of amine per acid group is employedin forming the salt. Generally the amine salt will be recovered as aviscous liquid.

Illustrative preferred compounds of the present invention include theamine salts of di-(oxyethylenated alkylphenol)-dithiophosphatescontaining from 2 to 15 oxyethylene groups. The preferred amines includestearyl amine and oleyl amine as illustrative of the fatty acid amines,N-tallow-1,3-diaminopropane as illustrative of theN-alkyl-diaminoalkanes, and the reaction products of carbon disulfidewith N,N-dioctyl-ethylenediamine, with N ,N -dioctyl-diethylenetriamineor with N ,N -triethylenetetramine as illustrative of the carbondisulfideamine reaction product. Preferred di-(oxyethylenatedalkylphenol)-dithiophosphates for use in preparing the amine saltsinclude di-(oxyethylenated octylphenol)-dithiophosphate containing fromtwo to fifteen oxyethylene groups, di (oxyethylenated dioctylphenol)dithiophosphate containing from two to fifteen oxyethylene groups, di(oxyethylenated nonylphenol) dithiophosphate containing from two tofifteen oxyethylene groups, di-(oxyethylenated dinonylphenol)-dithiophosphate containing from two to fifteen oxyethylene groups,di-(oxyethylenated decylphenol)-dithiophosphate containing from two tofifteen oxyethylene groups, di-(oxyethylenateddidecylphenol)-dithiophosphate containing from two to fifteenoxyethylene groups, di-(oxyethylenated undecylphenol)- dithiophosphatecontaining from two to fifteen oxyethylene groups, di-(oxyethylenateddiundecylphenol)-dithiophosphate containing from two to fifteenoxyethylene groups, di (oxyethylenated dodecylphenol) dithiophosphatecontaining from two to fifteen oxyethylene groups, di (oxyethylenateddidodecylphenol) dithiophosphate containing from two to fifteenoxyethylene groups, etc., corresponding di (oxypropylenatedalkylphenol)-dithiophosphates, etc. As hereinbefore set forth, the alkylgroup or groups attached to the phenyl ring preferably are of primary orsecondary configuration.

Preferred di-(oxyalkylenated aliphatic alcohol)-dithiophosphates for usein forming the amine salts include di (oxyethylenated decanol)dithiophosphate, di-(oxyethylenated undecanol)-dithiophosphate,di-(oxyethylenated dodecanol) dithiophosphate, di (oxyethylenatedtridecanol)-dithiophosphate, di-(oxyethylenatedtetradecanol)-dithiophosphate, di-(oxyethylenated pentadecanol)-dithiophosphate, di-(oxyethylenated hexadecanol)-dithiophosphate,di-(oxyethylenated heptadecanol)-dithiophosphate, di-(oxyethylenatedoctadecanol)dithiophosphate, di-(oxyethylenated nonadecanol)dithiophosphate, di- (oxyethylenated eicosanol) -dithiophosphate,di-(oxyethylenated heneicosanol)-dithiophosphate, di-(oxyethylenateddocosanol) dithiophosphate, di (oxyethylenated tricosanol)dithiophosphate, di (oxyethylenated tetracosanol) dithiophosphate, di(oxyethylenated pentacosanol) dithiophosphate, di (oxyethylenatedhexacosanol) dithiophosphate, di (oxyethylenated heptacosanol)dithiophosphate, di (oxyethylenated octacosanol) dithiophosphate, di(oxyethylenated nonacosanol)-dithiophosphate, di- (oxyethylenatedtriacontanol)-dithiophosphate, etc., corresponding di-(oxypropylenatedalkanol)-dithiophosphates, etc.

Conveniently the final product is recovered as a solution in a suitablesolvent and is used in this manner as an additive to an organicsubstrate. However, when the product is recovered in the absence of asolvent or when the product is not sufficiently soluble in thesubstrate, the desired solubility may be obtained by dissolving thecompound in a mutual solvent. Suitable solvents for this purposecomprise phenols and particularly alkylphenols or 'ployalkylphenols inwhich the alkyl groupor groups contain from six to twenty carbon atoms.The phenol may be used in a concentration from from about and preferablyfrom about 25% to about 500% by weight, and more particularly from about30% to about 200% by weight of the product of the present invention.

The amine salt of the oxyalkylenated hydroxyhydrocarbon thiophosphatewill have varied utility and is useful as an additive to organicsubstrates which undergo oxidative deterioration. In addition, theadditive serves as a detergent-dispersant, peroxide decomposer, etc.Organic substrates includes gasoline, naphtha, kerosene, jet fuel,lubricating oil, diesel fuel, fuel oil, residual oil, drying oil,grease, wax, resin, plastic, rubber, etc.

The amine salt of the oxyalkylenated hydroxyhydrocarbon thiophosphate isadvantageously used as an additive in lubricating oil, particularly whenthe lubricating oil is subjected to extreme temperature conditions. Thelubricating oil may be of natural or synthetic origin. The mineral oilsinclude those of petroleum origin and are referred to as motorlubricating oil, railroad type lubricating oil, marine oil, transformeroil, turbine oil, differential oil, diesel lubricating oil, gear oil,cylinder oil, specialty products oil, etc. Other natural oils includethose of animal, marine or vegetable origin.

The lubricating oils generally have a viscosity Within the range of fromSUS at 100 F. to 1000 SUS at 210 F. (SAE viscosity numbers include therange from SAE 10 to SAE 160). The petroleum oils are obtained fromparafiinic, naphthenic, asphaltic or mixed base crudes. When highlyparaflinic lubricating oils are used, a solubilizing agent also is used.

Synthetic lubricating oils are of varied types including aliphaticesters, polyalkylene oxides, silicones, esters of phosphoric and silicicacids, highly fluorine-substituted hydrocarbons, etc. Of the aliphaticesters, di-(Z-ethylhexyl) sebacate is being used on a comparativelylarge commercial scale. Other aliphatic esters include dialkyl azelates,dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkylglutarates, etc. Specific examples of these esters include dihexylazelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate,di-3,5,5-trimethylpentyl glutarate, di-(2-ethylhexyl) pimelate,di-(Z-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritoltetracaproate, dipropylene glycol dipelargonate,1,5-pentanedioldi-(2-ethylhexanonate), etc. The polyalkylene oxidesinclude polyisopropylene oxide, polyisopropylene oxide diether,polyisopropylene oxide diester, etc. The silicones include methylsilicone, methylphenyl silicone, etc., and the silicates include, forexample, tetraisooctyl silicate, etc. The highly fluorinatedhydrocarbons include fluorinated oil, perfluorohydrocarbons, etc.

Additional synthetic lubricating oils include (1) neopentyl glycolesters, in which the ester group contains from three to twelve carbonatoms or more, and particularly neopentyl glycol propionates, neopentylglycol butyrates, neopentyl glycol caproates, neopentyl glycolcaprylates, neopentyl glycol pelargonates, etc., (2) trimethylol alkanessuch as trimethylol ethane, trimethylol propane, trimethylol butane,trimethylol pentane, trimethylol hexane, trimethylol heptane,trimethylol octane, trimethylol decane, trimethylol undecane,trimethylol dodecane, etc., as well as the esters thereof andparticularly triesters in which the ester portions each contain fromthree to twelve carbon atoms and may be selected from those hereinbeforespecifically set forth in connection with the discussion of theneopentyl glycol esters, and (3) tricresylphosphate, trioctylphosphate,trinonylphosphate, tridecylphosphate, as well as mixed aryl and alkylphosphates, etc.

The present invention also is used in the stabilization of greases madeby compositing one or more thickening agents with an oil of natural orsynthetic origin. Metal base synthetic greases are further classified aslithium grease, sodium grease, calcium grease, barium grease, strontiumgrease, aluminum grease, etc. These greases are solid or semi-solid gelsand, in general, are prepared by the addition to the lubricating oil ofhydrocarbon soluble metal soaps or salts of higher fatty acids as, forexample, lithium stearate, calcium stearate, aluminum naphthenate, etc.The grease may contain one or more thickening agents such as silica,carbon black, talc, organic modified bentonite, etc., polyacrylates,amides, polyamides, aryl ureas, methyl N-n-octadecyl terephthalomate,etc. Another type of grease is prepared from oxidized petroleum wax, towhich the saponifiable base is combined with the proper amount of thedesired saponifying agent, and the resultant mixture is processed toproduce a grease. Other types of greases in which the features of thepresent invention are usable include petroleum greases, whale grease,wool grease, etc., and those made from inedible fats, tallow, butcherswaste, etc.

Oils of lubricating viscosity also are used as transmission fluids,hydraulic fluids, industrial fluids, etc., and the novel features of thepresent invention are used to further improve the properties of theseoils. During such use the lubricity properties of the oil are important.Any suitable lubricating oil which is used for this purpose is improvedby incorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rollingoils, soluble oils, drawing compounds, etc. In this application, the oilis used as such or as an emulsion with water. Here again, it is desiredthat the oil serves to lubricate the metal parts of saws, knives,blades, rollers, etc., in addition to dissipating the heat created bythe contact of the moving metal parts.

Oils of lubricating viscosity also are used as slushing oils. Theslushing oils are employed to protect finished or unfinished metalarticles during storage or transportation from one area to another. Themetal articles may be of any shape or form including steel sheets,plates, panels, coils, bars, etc., which may comprise machine parts,engines, drums, piston rings, light arms, etc., as well as farmmachinery, marine equipment, parts for military or other vehicles,household equipment, factory equipment, etc. A coating which may bevisible to the eye, or not, as desired, covers the metal part andprotects it from corrosion, etc.

The concentration of the amine salt of the oxyalkylenatedhydroxyhydrocarbon thiophosphate to be employed as an additive willdepend upon the particular substrate in which it is to be used. Ingeneral, the additive is used in a concentration of from about 0.001% toabout 25% by weight of the substrate and preferably within the range offrom about 0.01% to about 5% by weight of the substrate. When used inconventional lubricating oil, the additive generally may be employed ina concentration of from about 0.01% to about 2% by weight of the oil.When used in lubricating oil for more severe operations, such as hypoidgear oil, the additive is used in a concentration of from about 1% toabout 20% or more by weight of the oil. In general, substantially thesame range of additive concentration is employed when the oil is used astransmission fluid, hydraulic fluid, industrial fluid, etc. When the oilis used in the formulation of a grease, the additive is used in aconcentration of from about 0.5% to 5% by weight of the oil. When usedin cutting oil, rolling oil, soluble oil, drawing compound, etc., theadditive may be used in a concentration of from about 0.1% to about 10%by weight of the oil. When used in slushing oil, the additive may beused in a concentration of from about 0.1% to about 15% by weight ormore of the oil.

It is understood that the additive of the present invention may be usedalong with other additives incorporated in the organic substrate. Theother additives will depend upon the particular organic substrate. Forexample, in lubricating oil, the additional additives may comprise oneor more of viscosity index improver, pour point depressor, anti-foamadditive, detergent, corrosion inhibitor, additional antioxidant, etc.Preferred additional antioxidants are of the phenolic type and includetertiarybutylcatechol, 2,6-ditertiarybutyl-4-methylphenol,2,4-dimet-hyl-6-tertiarybutylphenol, etc.,2-tertiarybutyl-4-methoxyphenol, 2- tertiarybutyl-4-ethoxyphenol, etc.

The amine salt of the present invention is an emulsifying agent and,therefore, will serve to emulsify water and oil of lubricating viscosityfor use as lubricating oil, slushing oil, cutting oil, rolling oil,soluble oil, drawing compound, etc. When desired, an additionalemulsifying agent may be employed. Any suitable emulsifying agent can beused, including alkali metal sulfonates of petroleum sulfonic acids,mahogany sulfonates, naphthenic acids, fatty acids, etc., fatty alcoholsulfonates, pentaerythritol oleates, laurates, etc. The amount of waterused in the emulsified oils will depend upon the particular use of theemulsion and may range from 0.25% to 50% or even up to 98% by weight ofthe composition.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

Example I The compound of this example is theN-tallow-1,3-diaminopropane salt of di-(oxyethylenated nonylphenol)-dithiophosphate containing one oxyethylene group per each nonylphenylgroup. The di-(oxyethylenated nonylphenol)-dithiophosphate was preparedby charging 528 g. (2 moles) of oxyethylenated nonylphenol containingone oxyethylene group and benzene into a reaction flask and thenstirring and heating the mixture to 140 F. At this temperature and withstirring, 111 g. (0.5 mole) of P S were added gradually over a period of2.5 hours. During the addition of the P 8 the temperature rose slowly toabout 165 F. Stirring and heating to about 195 F. were continued for anadditional two hours. Following completion of the reaction, the reactionflask was cooled and then filtered to remove any unreacted P S Thefiltrate was then distilled under vacuum to remove the benzene solvent.The di-(oxyethylated nonylphenol)-dithiophosphate was recovered as aliquid of medium viscosity. Analyses showed a sulfur content of 9.28%which corresponds to the theoretical sulfur content of 10.3% and aphosphorus content of 4.12% which corresponds to the theoreticalphosphorus content of 5%.

The amine salt of the dithiophosphate prepared as described in theprevious paragraph was formed by mixing, on an equivalent weight basis,75 g. of the di-(oxy- Example II The compound of this example is theoleyl amine salt of the di-(oxyethylenated nonylphenol)-dithiophosphatecontaining one oxyethylene group per each nonylphenyl group. Thedi-(oxyethylenated nonylphenol)-dithioph0sphate was prepared asdescribed in Example I. This reaction was effected by mixing equivalentweights of the reactants which, in this case, were 25 g. of thisdithiophosphate and 11.7 g. of oleyl amine. The reactants were mixed atroom temperature and the oleyl amine salt of di-(oxyethylenatednonylphenol)-dithiophosphate was recovered as a viscous liquid of ambercolor having a viscosity of 4400.3 centistokes at F. measured accordingto ASTM method D445.

Example III The compound of this example was prepared using an amineformed by reacting N ,N -bis-(1-ethyl-3-methylpentyl)-diethylenetriaminewith carbon disulfide and then reacting the resultant amine with thedi-(oxyethylenated nonylphenol)-dithiophosphate prepared in the mannerdescribed in Example I. The reaction of the N ,N -bisdiethylenetriaminewith carbon disulfide was effected by dissolving 327 g. (1 mole) of thetriamine in 500 cc. of xylene and slowly adding 76 g. (1 mole) of carbondisulfidethereto with vigorous stirring. The mixture then was stirredand heated to refluxing until the evolution of hydrogen sulfide ceased.After completion of the reaction, the solvents were removed by vacuumdistillation. The product had a neuralization equivalent of 359.7 whichcorresponds to the calculated neutralization equivalent of 369.7.

The amine salt was prepared by mixing, on an equivalent weight basis,15.6 g. of the triamine-carbon disulfide reaction product and 25 g. ofdi-(oxyethylenated nonylphenol)-dithiophosphate prepared as described inExample I. The mixing was effected at room temperature, but heat wasgenerated due to the exothermicity of the reaction. The amine salt wasrecovered as a viscous liquid of amber color having an index ofrefraction 11 of 1.53807.

Example IV The compound of this example is the N-tallow-1,3-diaminopropane salt of di-(oxyethylenated nonylphenol)- dithiophosphatecontaining five oxyethylene groups per each nonylphenyl group. Thedi-(oxyethylenated nonylphenol)-dithiophosphate was prepared insubstantially the same manner as hereinbefore described and wasrecovered as a fluid oil having a refractive index n of 1.5055 and asulfur analysis of 4.29% by weight which corresponds to the theoreticalsulfur content of 4.62%.

The amine salt was prepared by mixing 1.8 g. (0.01 mole) of theN-tallow-1,3-diarninopropane with 8.6 g. (0.01 mole) of thedi-(oxyethylenated nonylphenol)- dithiop=hosphate at room temperature.The salt was re covered as a viscous liquid of amber color.

Example V The compound of this example is theN-tallow-1,3-diaminopropane salt of di-(oxyethylenated nonylphenol)-dithiophosphate having an average of 12 to 13 oxyethylene groups pereach nonylphenyl group. The salt was prepared by the room temperaturemixing of 1.8 g. (0.01 mole) of N-tallow-1,3 diaminopropane with 15.9 g.(0.01 mole) of di-oxyethylenated nonylphenol)-dithiophosphate having anaverage of 12 to 13 oxyethylene groups. The salt was recovered as aviscous liquid of amber color having an index of refraction 11 of1.49725.

Example VI The oleyl amine salt of di-(oxyethylenated nonylphenoldithiophosphate containing five oxyethylene groups per each nonylphenylgroup was prepared in substantially the same manner as describedherein-before by intimately mixing, at room temperature, 2.7 g. (0.01mole) of oleyl amine with 8.6 g. (0.01 mole) of the di- (oxyethylenatednonylphenol)-dithiophosphate. The salt was recovered as a viscous liquidof amber color having an index of refraction n of 1.51173.

1 1 Example VII The oleyl amine salt of di-(oxyethylenatednonylphenol)-dithiophosphate, containing an average of 12 to 13oxyethylene groups per each nonylphenyl group, was prepared insubstantially the same manner as described hereinbefo're by intimatelymixing, at room temperature, 2.7 g. (0.01 mole) of oleyl amine with 13.2g. (0.01 mole) of the di-(oxyethylenated nonylphenol)-dithiophosphate.The salt was recovered as a viscous liquid of amber color.

Example VIII The amine salt of this example is prepared by mixing, atroom temperature, 3.6 g. (0.01 mole) of the triaminecarbon disulfidereaction product, prepared as described in Example III, with 8.6 g.(0.01 mole) of di-(oxyethylenated nonylphenol)-dithiophosphatecontaining five oxyethylene groups per each nonylphenyl group. The saltis recovered as a viscous liquid of amber color having a refractiveindex 11, of 1.52372.

Example IX The compound of this example is the triamine-carbon disulfidesalt of di-(oxyethylenated nonylphenol)-dithiophosphate having anaverage of 12 to 13 oxyethylene groups per each nonylphenyl group. Thetriamine-carbon disulfide reaction product was prepared as described inExample III. This salt was prepared by mixing, at room temperature, 3.6g. (0.01 mole) of the triamine-carbon disulfide reaction product with15.9 g. (0.01 mole) of the di-(oxyeth'ylenatednonylphenol)-dithiophosphate. The salt was recovered as a viscous liquidof amber color.

Example X The compound of this example is theN-tallow-1,3-diaminopropane salt of di-(oxyethylenated octylphenol)-dithiophosphate having an average of 9 to 10 oxyethylene groups per eachoctylphenyl group. This salt was prepared by mixing, at roomtemperature, 1.8 g. (0.01 mole) of N-tallow-1,3-diaminopropane with 13.2g. (0.01 mole) of the di-(oxyethylenated octylphenol)-dithiophosphate.The resulting salt was recovered as a viscous liquid of amber colorhaving a refractive index 11 of 1.50806.

Example XI The oleyl amine salt of the di-(oxyethylenatedoctylphenol)-dithiophosphate, having an average of 9 to 10 oxythylenegroups per each octylphenyl group, was prepared by mixing, at roomtemperature, 2.7 g. (0.01 mole) of oleyl amine with 13.2 g. (0.01 mole)of the di-(oxyethylenated octylphenol)-dithiophosphate and recoveringthe resultant salt as a viscous liquid of amber color having a viscosityof 990.9 centistokes at 74 F. measured in accordance with ASTM methodD445.

Example XII The amine salt of this example was prepared by mixing, atroom temperature, 3.6 g. (0.01 mole) of the triamine-carbon disulfidereaction product described in Example III with 13.2 g. (0.01 mole) ofdi-oxyethylenated octylphenol)-dithiophosphate having an average of 9 to10 oxyethylene groups per each octylphenyl group. The resulting salt wasrecovered as a viscous liquid of amber color having a viscosity of2223.3 centistokes at 76 F. measured in accordance with ASTM methodD445.

Example XIII The compound of this example is the oleyl amine salt ofdi-(oxyethylenated dinonylphenol) dithiophosphate having eightoxyethylene group per each nonylphenyl group. This salt was prepared bymixing, at room temperature, 2.7 (0.01 mole) of oleyl amine with 14.1 g.(0.01 mole) of di-(oxyethylenated dinonylphenol)-dithiophosphate havingeight oxyethylene groups, and recovering the salt as a viscous liquid ofamber color.

12 Example XIV The compound of this example is the N ,N -bis-(1-ethyl-3-methylpentyl) -diethylenetriamine salt of di- (oxyethylenatednonylphenol) dithiophosphate having four oxyethylene groups per eachnonylphenyl group. This salt was prepared by mixing, at roomtemperature, 9.6 g. (0.1 mole) of di-(oxyethylenated nonylphenol)-dithiophosphate having four oxyethylene groups with 10.86 g. (0.033mole) of the N ,N -dioctyl-diethylenetriamine. The temperature of mixingrose to a maximum of about F. and the salt was recovered as a viscousliquid of medium amber color.

Example XV The N ,N -dioctyl-diethylenetriamine salt ofdi-(oxyethylenated nonylphenol)-dithiophosphate having eight oxyethylenegroups per each nonylphenyl group was prepared by mixing, at roomtemperature, g. (0.1 mole) of the di-(oxyethylenatednonylphenol)-dithiophosphate with 10.86 g. (0.033 :mole) of the N ,Ndioctyl-diethylenetriamine. The temperature rose to a maximum of about115 F. and the salt was recovered as a heavy viscous liquid having aslight amber color. The N ,N -dioctyl-diethylenetriamine used in thisexample is the same as described in Example XIV.

Example XVI The compound of this example was prepared by mixing at roomtemperature, 10.86 g. (0.033 mole of the N ,Ndioctyl-diethylenetriamine, described in Example XIV, with 169.4 g. (0.1mole) of di-(oxyethylenated nonylphenol)-dithiophosphate having anaverage of 12 to 13 oxyethylene groups per each nonylphenyl group. Thetemperature rose to a maximum of about 108 F., and the salt wasrecovered as a heavy viscous liquid having a slight amber color.

Example XVII The compound of this example is theN-soya-1,2-diaminoethane salt of di-(oxypropylenated dodecylphenol)-dithiophosphate containing two oxypropylene groups per eachdodecylphenyl group. The amine salt is prepared by commingling, at roomtemperature, equal mole proportions of the N-soya-1,2-diaminoethane anddi-(oxypropylenated dodecylphenyl)-dithiophosphate. The resulting saltis recovered as a viscous liquid of amber color.

Example XVIII The salt of thi example is prepared by mixing, at roomtemperature, equal mole proportions of N,N'-dioctylamino-diphenylmethanewith di (oxyethylenated decanol)-dithiophosphate having an average ofsix oxyethylene groups per each decyl group. The salt is recovered as aviscous liquid of amber color.

Example XIX As hereinbefore set forth, the compounds of the presentinvention are of especial utility as additives in lubricating oils. Onemethod of evaluating lubricating oils is by the Falex machine. Thisprocedure is described in detail in a book entitled Lubricant Testingauthored by E. G. Ellis and published by Scientific Publications (GreatBritain) Limited, 1953, pages -154. Briefly, the Falex machine consistsof a rotating pin which runs between two V shape bearings which arespring loaded against the pin and provided with means for varying theload. The oil to be tested is poured into a metal trough in which thepin and bearings are partly submerged. The machine was operated for fiveminutes each at 250 and 500 pound loads and then forty-five minutes at750 pound load and, in some evaluations, up to 1000 pound or 1500 poundloads. The data collected includes the temperature of the oil at each ofthe loads and the torque in pounds per square inch at each load, as wellas the wear which is determined by a ratchet wheel arrangement in whichthe teeth are advanced in order to maintain the desired load. Each toothis equivalent to approximately 0.000022 inch. Preferred additives arethose 14 as Games 340 White Oil. Typical specifications of this oilinclude the following:

which impart low temperature, low torque and low wear Distillationrange, F. 740-975 t the l- Specific gravity at 60 F 0.8836

'In another series of tests the machine was operated for Vi i fiveminutes at each load from 250 pounds to seizure 100 F 360 at 250 poundincrements. The maximum load and the 210" 52.2 time in minutes at thisload to seizure are reported, as Fl h point, OG 440 well as thetemperature of the oil. In this case the higher p point, a 2 temperatureis preferred because it means that the oil R f a ti index at 1,4805 1soperatmg sa tlsfactonly at a hlgher temperature saybolt 1 +30 Thelubricatmg oil used 1n this example is dioctyl iz zgg gz 011 marketedunder the trade some of the additives were not readily soluble in theRun 1 in the following table is a run made using white 011 and,accordingly, were solublhzed by cornmm- Plexol not containing anadditive and thus is the blank ghng. nonylphenol therewlth and heatmgand Surfing as or control run. requlred' Run 2 is a run made usinganother Sample of Run No. 7 1n the followmg table s a run made us1ng 3 5to which had been added two percent by Weight the white 011 notconta1n1ng an add 1t1ve and thus 1s the of theN-tallow-1,3-diaminopropane salt of di-(oxyethylblank or enatednonylphenol)-dithiophosphate containing one oxy- R N 8 a run madeanother Sample Of the ethylene. group prepared as described in Example1, white 011 to which had been added two percent by welght Run No. 3 isa run made using another sample of the i i' g i g salt xyethyl- Plexolto which had been added two percent by weight enated nony pheno lthloposphate contammg an y of the oleyl amine salt of di-(oxyethylenatednonylphe- W of 12 to 13 oxyethylene groups Prepared as descnbednol)-dithiophosphate containing one oxyethylcne group In Exampleprepared as described in Example IL Iiun No. 9 1s a run made usinganother sample of the Run No. 4 is a run made using another Sample ofwhlte 011 to wh1ch had been added two percent by welght to which hadbeen added two percent by Weight of the oleyl amlne saltotdi-(oxyethylenated nonylphenol) of the N ,N -diaminopropane salt ofdi-(oxyethylenated dlthlophosphate con/taming an aveiage 9 12 to 13nonylphenol)-dithiophosphate containing five oxyethylcne ethylene groupsPrepared as descnbed m Example groups prepared as d ib d i E l 1V RunNo. 10 is a run made using another sample of the {Run N0, 5 is a runmade using another ample of White Oil to which had been added tWOpercent by weight P161101 to which had been added two percent by eight0f the triamine-carbon disulfide salt Of til-(OXYfithYlEl'lZtfid of theoleyl amine salt of di-(oxyethylenated nonylnonylphenol)-dithiophosphatecontaining an average of phenol)-dithiophosphate containing fiveoxyethylcne 12 to 13 oXyethylene groups P p as described in groupsprepared as described in Example VI. Example IX.

Run No. 6 i a run made using another sample of Run No. 11 is a run madeusing another sample of the Plexol to which had been added two percentby weight white oil to which had been added two percent by weight of theN-tallow-1,3-diaminopropane salt of di-(oxyethylof theN-tallow-1,3-diaminopropane salt of di-(oxyenatedoctylphenol)-dithiophosphate containing an averethylenatedoctylphenol)-dithiophosphate containing an age of 9 to 10 oxyethylcnegroups prepared as described average of 9 to 10 oxyethylcne groupsprepared as dein Example X. scribed in Example X.

TABLE I Temperature, F. Torque, lbs. Wear, Teeth Seizure Conditions RunNo.

250 500 750 1,000 250 500 750 1,000 250 500 750 1,000 Load Time Temperature, F-.

SSeizure.

From the data in the above table, it will be seen that Run No. 12 is arun made using another sample of the the dioctyl sebacate withoutadditive (Run No. 1) underwhite oil to which had been added two percentby weight went seizure at a load of 750 pounds. In contrast, seizure ofthe oleyl amine salt of di-(oxyethylenated octylphenol) conditions forthe samples of the dioctyl sebacate condithiophosphate containing anaverage of 9 to 10 oxytaining the compounds of the present inventionwere ethylene groups prepared as described in Example XI.

Run No. 13 is a run made using another sample of the from 1250 to 1500pounds.

Example XX lubricating oil was a mineral oil marketed commercially whiteoil to which had been added two percent by weight of the triamine-carbondisulfide salt of di-(oxyethylenated octylphenol)-dithiophosphatecontaining an average of 9 to 10 oxyethylcne groups prepared asdescribed in Example XII.

TABLE II Temperature, F. Torque, lbs. Wear, Teeth Seizure Conditions RunNo.

250 500 750 250 500 750 250 500 750 Load Time Temperature, F.

172 350-8 5-6 30-S S 425 0.1 275 192 278 364 4-6 10-15 13-18 0 0 31 1,325 0v 1 450 185 265 375 4-5 10-11 13-17 0 0 33 1, 500 0. 5 450 164 264388 4-5 -11 -20 0 0 6 1, 250 0. 1 400 175 285 375 3-5 10-13 12-20 0 0 221, 250 0. 4 425 164 267 357 4-5 10-13 13-17 0 O 37 1, 225 0. 1 400 180285 405 5 11-12 14-18 0 0 30 1, 250 2. 2 435 SSeizure.

From the above data, it will be noted that the oil without additive (RunNo. 7) underwent seizure at a load of 425 pounds. In contrast, the whiteoil containing the additive of the present invention did not undergoseizure until loads of from 1225 to 1500 pounds.

Example XXI Example XXII Because the amine salts of the presentinvention are more thermally stable than the dithiophosphates, anotherseries of evaluations were made in substantially the same manner asdescribed in Example XIX, except that the machine was operated for fiveminutes each at 250, 500,

Run No. 16 is a run made using another sample of the Hercules J64 oil towhich had been added two percent by weight of the oleyl amine salt ofdi-(oxyethylenated nonylphenol)-dithiophosphate containing fiveoxyethylene groups prepared as described in Example VI.

Run No. 17 is a run made using another sample of the Hercules J64 oil towhich had been added two percent by weight of the triamine-carbondisulfide salt of di-(oxyethylenated nonylphenol)-dithiophosphatecontaining five oxyethylene groups prepared as described in ExampleVIII.

Run No. 18 is a run made using another sample of the Hercules J64 oil towhich had been added two percent by weight of the oleyl amine salt ofdi-(oxyethylenated octylphenol)-dithiophosphate containing an average of9 to 10 oxyethylene groups prepared as described in Example XI.

Run No. 19 is a run made using another sample of the TABLE IIITemperature, F. Torque, lbs. Wear,Teeth Run No.

750, 1000 and 1250 loads and then for forty-five minutes at 1500 load.It is readily seen that this is a much more severe evaluation than thosereported in the previous examples. Also, these evaluations were madeusing pentaerythritol ester lubricating oil which is marketedcommercially as Hercules J64.

When evaluated in the manner previously described, the Hercules J64 oilwithout additive had a seizure load of 1000 pounds. Results of variousruns using other samples of this oil Containing additives of the presentinvention are reported in the following table.

Run No. 14 is a run made using another sample of the Hercules J 64 oilto which had been added two percent by weight of theN-tallow-1,3-diaminopropane salt of di-(oxyethylenatednonylphenol)-dithiophosphate containing five oxyethylene groups preparedas described in Example IV.

Run No. 15 is a run made using another sample of the Hercules J64 oil towhich had been added two percent by weight of theN-tallow-l,3-diaminopropane salt of di-(oxyethylenatednonylphenol)-dithiophosphate containing an average of 12 to 13oxyethylene groups prepared as described in Example V.

From the data in the above table, it will be seen that the additives ofthe present invention were effective in inhibiting seizure even at thehigh load of 1500 pounds when evaluated in this oil.

Example XXIII The N-tallow-1,3-diaminopropane salt of di-(oxyethyla.

enated nonylphenol)-dithiophosphate containing five oxyethylene groups,prepared as described in Example IV, is used in a concentration of 0.5%by weight as an additive in grease. The additive is incorporated in acommercial Mid-Continent lubricating oil having an S.A.E. viscosity of20. Approximately 92% of the lubricating oil then is mixed withapproximately 8% by weight of lithium stearate. The mixture is heated toabout 450 F., with constant agitation. Subsequently, the grease iscooled, while agitating, to approximately 250 F., and then the grease isfurther cooled slowly to room temperature.

The stability of the grease is tested in accordance with ASTM D-942method, in which method a sample of the grease is placed in a bomb andmaintained at a temperature of 250 F. Oxygen is charged to the bomb, andthe time required for a drop of five pounds pressure is taken as theinduction period. A sample of the grease without additive will reach theinduction period in about eight hours. On the other hand, a sample ofthe grease containing 0.3% by weight of the additive of the presentinvention will not reach the induction period for more than 100 hours.

We claim as our invention:

1. Amine salt of oxyalkylenated hydroxyhydrocarbon .thiophosphatecontaining one or two oxyalkylenated hydroxyhydrocarbon radicals permolecule, said radical or radicals containing a chain of from 1 to 40oxyalkylene groups linking the hydroxyhydrocarbon with the phosphorusatom.

2. Amine salt of oxyalkylenated hydroxyhydrocarbon dithiophosphatecontaining one or two oxyalkylenated hydroxyhydrocarbon radicals permolecule, said radical or radicals containing a chain of from 1 to 40oxyalkylene groups linking the hydroxyhydrocarbon with the phosphorusatom.

3. Amine salt of oxyalkylenated alkylphenol dithiophosphate containingone or two oxyalkylenated alkylphenol radicals per molecule, saidradical or radicals containing a chain of from 1 to 40 oxyalkylenegroups linking the alkylphenol With the phosphorus atom.

4. Amine salt of di-(oxyalkylenated alkylphenol)dithiophosphate, each ofthe two oxyalkylenated alkylphenol radicals containing a chain of from 1to 40 oxyalkylene groups linking the alkylphenol with the phosphorusatom.

5. Amine salt of di-(oxyethylenated alkylphenol)dithiophosphate, each ofthe two oxyethylenated alkylphenol radicals containing a chain of from 1to 40 oxyethylene groups linking the alkylphenol with the phosphorusatom.

6. N-alkyl-diaminoalkane salt of di-(oxyalkylenatedalkylphenol)-dithiophosphate, each of the two oxyalkyl- 18 enatedalkylphenol radicals containing a chain of from 1 to oxyalkylene groupslinking the alkylphenol with the phosphorus atom.

7. N-tallow-1,3-diaminopropane salt of di-(oxyethylenatedoctylphenol)-dithiophosphate, each of the two oxyethylenated octylphenolradicals containing a chain of from 1 to 40 oxythylene groups linkingthe octylphenol with the phosphorus atom.

8. N-tallow-1,3-diamin-opropane salt of di-(oxyethylenatednonylphenol)-dithiophosphate, each of the two ox'yethylenatednonylphenol radicals containing a chain of from 1 to 40 oxyethylenegroups linking the nonylphenol with the phosphorus atom.

9. Fatty amine salt of di-(oxyalkylenated alkylphenol)- dithiophosphate,each of the two oxyalkylenated alkylphenol radicals containing a chainof from 1 to 40 oxyalkylene groups linking the alkylphenol with thephosphorus atom.

10. Oleyl amine salt of di-(oxyethylenated octylphenol)-dithiophosphate,each of the two oxyethylenated octylphenol radicals containing a chainof from 1 to 40 oxyethylene groups linking the octylphenol with thephosphorus atom.

11. Oleyl amine salt of di-(oxyethylenated nonylphenoD-dithiophos-phate,each of the two oxyethylenated nonylphenol radicals containing a chainof from 1 to 40 oxyethylene groups linking the nonylphenol with thephosphorus atom.

References Cited UNITED STATES PATENTS 3,002,014 9/ 1961 Dinsmore et al260-925 CHARLES B. PARKER, Primary Examiner.

BERNARD BILLIAN, Assistant Examiner.

1. AMINE SALT OF OXYALKYLENATED HYDROXYHYDROCARBON THIOPHOSPHATECONTAINING ONE OR TWO OXYALKYLENATED HYDROXYHYDROCARBON RADICALS PERMOLECULE, SAID RADICAL OR RADICALS CONTAINING A CHAIN OF FROM 1 TO 40OXYALKYLENE GROUPS LINKING THE HYDROXYHYDROCARBON WITH THE PHOSPHOROUSATOM.